CN115747573B - Cold spraying zinc alloy powder, coating and preparation method thereof - Google Patents
Cold spraying zinc alloy powder, coating and preparation method thereof Download PDFInfo
- Publication number
- CN115747573B CN115747573B CN202211572121.4A CN202211572121A CN115747573B CN 115747573 B CN115747573 B CN 115747573B CN 202211572121 A CN202211572121 A CN 202211572121A CN 115747573 B CN115747573 B CN 115747573B
- Authority
- CN
- China
- Prior art keywords
- powder
- coating
- cold
- alloy powder
- zinc alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 154
- 239000011248 coating agent Substances 0.000 title claims abstract description 147
- 239000000843 powder Substances 0.000 title claims abstract description 136
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 67
- 238000010288 cold spraying Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000007921 spray Substances 0.000 claims abstract description 61
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 50
- 239000000956 alloy Substances 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000889 atomisation Methods 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 25
- 239000003570 air Substances 0.000 claims description 24
- 239000012159 carrier gas Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005488 sandblasting Methods 0.000 claims description 5
- 238000012387 aerosolization Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 64
- 230000007797 corrosion Effects 0.000 abstract description 55
- 230000000694 effects Effects 0.000 abstract description 14
- 230000001105 regulatory effect Effects 0.000 abstract description 10
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 9
- 238000004210 cathodic protection Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 description 65
- 229910052725 zinc Inorganic materials 0.000 description 33
- 239000011777 magnesium Substances 0.000 description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 23
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005507 spraying Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 102220043159 rs587780996 Human genes 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910002058 ternary alloy Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Coating By Spraying Or Casting (AREA)
Abstract
The application relates to the technical field of metal corrosion protection and discloses cold spraying zinc alloy powder, a coating and a preparation method thereof, wherein the cold spraying zinc alloy powder is a mechanical mixed powder of ZnMg alloy powder and aluminum powder; the ZnMg alloy powder is prepared by adopting an air atomization powder preparation method, and Mg accounts for 0-4% of the mass fraction of the ZnMg alloy powder; the aluminum powder is prepared by adopting an air atomization powder preparation method; the aluminum powder accounts for 0-30% of the mass fraction of the cold spray zinc alloy powder. In the scheme, the self-corrosion potential of the coating can be reduced by adding Mg element, and the cathodic protection effect of the coating is enhanced; the content of ZnMg intermetallic compound is regulated and controlled by Mg element, the phase distribution in the coating is regulated and controlled by aluminum powder, and the reaction of aluminum element is promoted, so that the coating can rapidly and spontaneously generate a layered corrosion product layer with shielding effect in a corrosion medium, the service life of the coating serving as a sacrificial anode layer is prolonged, and the corrosion protection performance of the coating is enhanced.
Description
Technical Field
The application relates to the technical field of metal corrosion protection, and mainly relates to cold spraying zinc alloy powder, a coating and a preparation method thereof.
Background
With the continuous expansion of the development scale of ocean resources and the rapid development of the ocean resources towards open sea and deep sea, a large amount of steel materials are put into ocean engineering construction, however, the ocean environment has the characteristics of high temperature, high humidity, high salinity, long sunlight and the like, the steel corrosion problem in the environment is particularly serious, and great potential safety hazard and great economic loss are caused to ocean engineering. Among the numerous means of controlling corrosion failure of marine metal components, coating protection is most directly effective, particularly zinc coatings, which are widely used as marine environmental coating protection materials because of their lower corrosion potential relative to steel substrates, which provide both shielding and cathodic protection when applied to the steel surface.
The main modes for preparing the zinc coating at present are hot dip plating, organic coating, hot spraying, cold spraying and the like. The cold spraying is used as a novel surface coating technology, has the advantages of low temperature, high bonding strength and the like, and compared with the hot spraying, the cold spraying has the advantages of low oxygen content, high density and small thermal influence on a substrate; compared with the traditional zinc-rich coating, the coating has better weather resistance due to no organic component, and the special forming mechanism of the coating enables the interface bonding performance of the coating/substrate to be better. In addition, the construction of cold spraying is not limited by the size and shape of the workpiece, and the whole operation process is simple, convenient, safe and environment-friendly, so that the cold-sprayed zinc coating with high corrosion resistance has wide application prospect in corrosion protection of marine steel structures. However, since pure zinc generally has high electrochemical activity, zinc coating tends to undergo severe self-corrosion at the early stage of corrosion reaction, and the products are mostly porous ZnO and Zn (OH) 2 The loss of the zinc coating is fast, and the service life of the zinc coating is greatly shortened.
Aiming at the problems, the powder pretreatment or the coating post-treatment method is adopted to improve the protective performance of the coating at present, for example, patent CN 113088956A discloses a method for preparing Zn-G/Ni/Al based on low-pressure cold spraying 2 O 3 The preparation method of the corrosion-resistant coating is carried out by coating and passivating, and Zn-G/Ni/Al is sprayed on the coating in a cold spraying way in the passivating process 2 O 3 Surface acquisition of composite coating Zn 5 (OH) 8 Cl 2 And Zn 4 CO 3 (OH) 6 An isopipe layer to enhance corrosion of the coating itselfCorrosion protection performance; patent CN 113106439A discloses a preparation method of an anti-corrosion composite coating on the surface of a magnesium alloy, which comprises the steps of firstly carrying out pretreatment to grow a layer of LDH product on the surface of a magnesium alloy matrix in situ, and then carrying out cold spraying to prepare Zn-G/Ni/Al 2 O 3 The composite coating is formed, so that a multi-layer composite coating is constructed, and the corrosion resistance of the magnesium alloy is improved; patent CN 114182249A discloses a method for increasing corrosion resistance of a cold-sprayed double-layer coating, which is mainly realized by firstly cold-spraying Zn/Al on a substrate 2 O 3 Coating, spraying Al/Al again 2 O 3 Coating, and annealing the double-layer structure coating, passing through Al and Al on the surface layer 2 O 3 The corrosion protection performance of the coating is improved due to the characteristics of high stability and the properties of the sacrificial anode of the internal Zn coating; patent CN110144579B discloses a zinc-based composite coating with rapid repair capability and a preparation method thereof, wherein a mixture of reduced graphene oxide coated Zn powder and Al powder is used as a raw material in a pretreatment process, and then the zinc-based composite coating is prepared by a cold spraying method, so that the protective performance of the coating is enhanced by graphene. By adopting the method of the powder pretreatment or the coating post-treatment, the coating preparation steps are various and complex, and a plurality of inconveniences exist in practical application, especially for coating protection of large structural members such as ocean steel structures, the coating post-treatment has great difficulty.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned prior art deficiency, the purpose of this application is to provide a cold spray zinc alloy powder, coating and its preparation method, adopt the cold spray zinc alloy powder that this application provided to carry out cold spray construction to the base member, the cold spray zinc alloy coating that obtains that prepares has excellent protective effect, need not extra powder or the preliminary treatment of base member or the aftertreatment step of coating, aim at solving the loaded down with trivial details problem of current coating preparation step.
The technical scheme of the application is as follows:
a cold spray zinc alloy powder, wherein the cold spray zinc alloy powder is a mechanically mixed powder of ZnMg alloy powder and aluminum powder;
the ZnMg alloy powder is prepared by adopting an air atomization powder preparation method, wherein Mg accounts for 0-4% of the mass fraction of the ZnMg alloy powder, and the mass fraction of Mg is not 0%;
the aluminum powder is prepared by adopting an air atomization powder preparation method;
the aluminum powder accounts for 0-30% of the mass fraction of the cold spray zinc alloy powder, and the mass fraction of the aluminum powder is not 0%.
By adopting the cold spraying zinc alloy powder provided by the application, the cold spraying zinc alloy powder can be used for cold spraying after being mechanically mixed with a specific amount of powder, and no additional pretreatment or post-treatment step of coating of powder or a base material is needed.
The cold spraying zinc alloy powder comprises 2-4% of Mg by mass of ZnMg alloy powder.
The Mg accounts for preferably 2 to 4% by mass of the ZnMg alloy powder, since the product is mostly a corrosion product of water-soluble magnesium when the Mg content is high, and less corrosion product of zinc adheres to the surface of the coating, which reduces the resistance of the coating.
The cold spraying zinc alloy powder comprises 5% -15% of aluminum powder by mass.
The cold spraying zinc alloy powder, wherein the average grain diameter of the ZnMg alloy powder is 20-50 mu m; the average particle diameter of the aluminum powder is 5-15 mu m.
The preparation method of the cold spraying zinc alloy powder comprises the following steps:
preparing ZnMg alloy powder and aluminum powder respectively by an aerosolization powder preparation method;
and mixing the ZnMg alloy powder and the aluminum powder in a mechanical stirring mode to obtain the cold spraying zinc alloy powder.
A preparation method of a cold spray zinc alloy coating comprises the step of preparing the cold spray zinc alloy coating on the surface of a substrate in a cold spray mode by adopting the cold spray zinc alloy powder.
The preparation method of the cold spraying zinc alloy coating comprises the step of performing low-pressure cold spraying.
The preparation method of the cold spraying zinc alloy coating comprises the steps of carrying out cold spraying, wherein carrier gas is one of compressed air, nitrogen or helium, the gas pressure is 0.5-0.8MPa, the carrier gas temperature is 200-600 ℃, the powder feeding speed is 0.5-2g/s, the distance between a spray gun and a base material is 6-20mm, and the moving speed of the spray gun is 200-600mm/min.
The preparation method of the cold spraying zinc alloy coating comprises the following steps before the cold spraying:
oil and rust removal is carried out on the surface of the base material;
and (3) carrying out sand blasting coarsening pretreatment on the surface of the base material, cleaning by using acetone or alcohol, and drying by cold air.
A cold spray zinc alloy coating, wherein the cold spray zinc alloy coating is prepared by the preparation method.
The beneficial effects are that: the cold spraying zinc alloy powder is a mechanical mixed powder of ZnMg alloy powder and aluminum powder, and the self-corrosion potential of the coating can be reduced by adding Mg element, so that the cathodic protection effect of the coating is enhanced; the content of ZnMg intermetallic compound is regulated and controlled by Mg element, the phase distribution in the coating is regulated and controlled by aluminum powder, and the reaction of aluminum element is promoted, so that the coating can rapidly and spontaneously generate a layered corrosion product layer with shielding effect in a corrosion medium, the service life of the coating serving as a sacrificial anode layer is prolonged, and the corrosion protection performance of the coating is enhanced.
Drawings
FIG. 1 is a SEM image of the cross-sectional morphology of a cold spray zinc coated substrate prepared in examples 1-3 and comparative example of the present application.
FIG. 2 is a graph showing the results of polarization curve tests after immersing the cold spray zinc coated substrates prepared in examples 1-3 and comparative examples of the present application in a corrosive medium for 0.5 h.
FIG. 3 is a Nyquist plot of the cold sprayed zinc coated substrates prepared in examples 1-3 and comparative examples of the present application after 24 hours of immersion in corrosive media.
FIG. 4 is a graph showing the phase angle test results of substrates with cold spray zinc coatings prepared in examples 1-3 and comparative examples of the present application after 24 hours of immersion in corrosive media.
Fig. 5 is an SEM image of the surface of the cold sprayed zinc coating prepared in example 2 of the present application after soaking the substrate in an etching medium for 24 hours.
Detailed Description
The application provides cold spraying zinc alloy powder, a coating and a preparation method thereof, and aims to make the purposes, the technical scheme and the effects of the application clearer and more definite, and the application is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In order to improve the service life of the cold spray zinc coating, a powder pretreatment or a coating post-treatment method is adopted at present, but the steps are various and complex, and a plurality of inconveniences exist in practical application, especially for coating protection of large structural parts such as marine steel structures, the coating post-treatment is difficult. Aiming at the problem, the application provides novel cold spraying zinc alloy powder based on a cold spraying technology from the angles of a corrosion mechanism and a protection mechanism of a coating.
Specifically, the cold spraying zinc alloy powder is a mechanically mixed powder of ZnMg alloy powder and aluminum powder;
wherein the ZnMg alloy powder is prepared by adopting an air atomization powder preparation method, the mass fraction of Mg accounts for 0% -4% of that of the ZnMg alloy powder, and the mass fraction of Mg is not 0%, preferably, the mass fraction of Mg accounts for 2% -4% of that of the ZnMg alloy powder;
the aluminum powder is prepared by adopting an air atomization powder preparation method;
the aluminum powder accounts for 0-30% of the mass fraction of the cold spray zinc alloy powder, and the mass fraction of the aluminum powder is not 0%, preferably the aluminum powder accounts for 5-15% of the mass fraction of the cold spray zinc alloy powder.
The cold spraying zinc alloy powder prepared by adopting the ZnMg alloy powder and the aluminum powder within the mass fraction range is easier to spontaneously generate an LDH product layer. In the application, znMg alloy powder and aluminum powder are prepared by an air atomization powder preparation method, and the powder prepared by air atomization is spherical powder, so that the follow-up mechanical mixing and the follow-up cold spraying are facilitated. In the application, the preferred average particle sizes of the ZnMg alloy powder and the aluminum powder are also provided, the average particle size of the ZnMg alloy powder is 20-50 mu m, the average particle size of the aluminum powder is 5-15 mu m, and the powder in the particle size range is adopted, so that the ZnMg alloy powder and the aluminum powder are convenient to uniformly mix, and the uniformity of the components of the prepared coating is ensured.
The applicant has found through long-term studies that the growth of LDH (layered double hydroxide ) and ZnMg intermetallic compound Zn in alloy coatings 2 Mg and Zn 11 Mg 2 Has a large relation with the distribution. In the technical scheme, from the perspective of uniformly distributing ZnMg intermetallic compounds, znMg alloy powder and aluminum powder are obtained by smelting-gas atomization powder preparation, and Zn in ZnMg alloy in the powder is regulated and controlled by the change of Mg content 2 Mg、Zn 11 Mg 2 Intermetallic compound content, primary Zn-rich phase eta and Zn/(Zn) 2 Mg/Zn 11 Mg 2 ) The binary eutectic structure optimizes the phase distribution in the coating by adding aluminum powder, thereby regulating and controlling the type and the relative content of corrosion products generated in the corrosion protection process, so that LDH and flake corrosion products Zn 5 Cl 2 (OH) 8 ·H 2 O can be generated on the surface of the coating preferentially and rapidly, so that the consumption rate of the coating is reduced, the cathodic protection action time of the coating is prolonged, and the corrosion protection performance of the cold spray zinc coating is improved. Moreover, by adopting the cold spraying zinc alloy powder provided by the application, the cold spraying zinc alloy powder can be used for cold spraying after only mechanically mixing a specific amount of powder, and no additional pretreatment or post-treatment step of coating of powder or a base material is needed.
Specifically, the preparation method of the cold spraying zinc alloy powder comprises the following steps:
preparing ZnMg alloy powder and aluminum powder respectively by an aerosolization powder preparation method;
and mixing the ZnMg alloy powder and the aluminum powder in a mechanical stirring mode to obtain mixed powder, namely the cold spraying zinc alloy powder.
In the application, fine aluminum powder is added in a mechanical mixing mode, so that the aluminum powder is uniformly distributed around the ZnMg alloy powder, and the phase distribution in the coating can be optimized.
Furthermore, the application also provides a preparation method of the cold spraying zinc alloy coating, wherein the cold spraying zinc alloy coating is prepared on the surface of the substrate by adopting the zinc alloy powder in a cold spraying mode and utilizing the characteristic of not changing the powder component and the structure in the cold spraying process.
Further, the cold spraying adopts a low-pressure cold spraying mode, the carrier gas can be one of compressed air, nitrogen or helium, the gas pressure is 0.5-0.8MPa, the carrier gas temperature is 200-600 ℃, the powder feeding speed is 0.5-2g/s, the distance between a spray gun and a substrate is 6-20mm, and the moving speed of the spray gun is 200-600mm/min. In the application, znMg alloy powder and Al powder belong to softer metals, and the powder utilization rate can be improved to the maximum extent by adopting the cold spraying parameters on the premise of ensuring that the coating has good binding force.
Further, before the cold spraying, the surface of the substrate is preferably subjected to a simple pretreatment, specifically comprising the following steps:
oil and rust removal is carried out on the surface of the base material;
and (3) carrying out sand blasting coarsening pretreatment on the surface of the base material, cleaning by using acetone or alcohol, and drying by cold air.
The degreasing and rust removal of the surface of the substrate is a conventional operation, and is not described herein.
The surface is subjected to sand blasting roughening pretreatment, so that the roughness of the surface of the substrate can be increased to improve the binding force of the coating. Brown corundum or white corundum can be adopted in the sand blasting coarsening pretreatment.
Further, the substrate may be a steel material. The steel is one of the main raw materials for ocean engineering construction, and the steel corrosion problem in the environment is particularly serious because the ocean environment has the characteristics of high temperature, high humidity, high salinity, long sunlight and the like, so that great potential safety hazard and great economic loss are caused for the ocean engineering. Forming the zinc alloy on the surface of the steel material by applying cold sprayingIn the corrosion process, the gold coating preferentially reacts due to the lower self-corrosion potential of the intermetallic compound, thereby forming an alkaline environment and promoting the Al in the area to be corroded and dissolved, so that LDH and Zn grow on the surface of the coating in situ 5 Cl 2 (OH) 8 ·H 2 And the sheet corrosion products such as O and the like improve the shielding effect of the coating on corrosive media and improve the protective performance of the coating.
The application provides a cold spray zinc alloy coating, which is formed by adopting the cold spray zinc alloy powder in a cold spray mode. The thickness of the cold sprayed zinc alloy coating may typically be 100-400 μm.
Compared with the prior art, the application has the following advantages:
the cold spray zinc alloy coating prepared by the method is essentially a sacrificial anode coating, and by special component design, on one hand, the self-corrosion potential of the coating is reduced by adding Mg element, and the cathodic protection effect of the coating is improved; meanwhile, by adding Al element, a uniformly covered LDH product layer can be rapidly generated at the initial stage of the corrosion reaction of the coating, and the flaky corrosion product Zn is promoted 5 Cl 2 (OH) 8 ·H 2 O is generated, and the shielding effect of the coating is improved. In addition, the cold spraying zinc alloy powder is prepared by physical mixing, and the coating is prepared by a cold spraying method, so that the components and the tissues of the coating are uniformly distributed, the coating is uniformly corroded in a corrosive medium, the serious local corrosion phenomenon is avoided, and the service life of the coating is prolonged.
The method mainly utilizes the low corrosion potential of ZnMg intermetallic compounds, can be rapidly dissolved in the early stage of corrosion, rapidly increases the local pH value and promotes the dissolution of Al, thereby generating protective corrosion products such as LDH and the like. Compared with ZnAlMg ternary alloy, the Zn/ZnMg binary eutectic structure in the ZnMg alloy has lower potential than the Zn/Al/ZnMg ternary eutectic structure, is more beneficial to promoting the dissolution of Al and rapidly generating protective corrosion products such as LDH and the like, can greatly reduce the consumption of Zn during corrosion protection, and prolongs the service life of the coating serving as a sacrificial anode coating. In addition, the ZnAlMg ternary alloy powder prepared by the gas atomization method generally belongs to the following stepsThe phase type of intermetallic compound in alloy component is relatively complex in cold process, and Zn is removed 2 Mg may be present in addition to Mg 4 Zn 7 、Al 12 Mg 17 The potential of the different phases is relatively close, and other phases can reduce Zn 2 The reaction rate of Mg as anode is unfavorable for the rapid increase of initial local pH and dissolution process of Al. In the scheme, different phases in the binary eutectic structure of the ZnMg alloy powder are relatively fewer, the phase composition is simpler, and because of the limitation of binary components, ternary intermetallic compounds do not exist, thus being beneficial to the Zn of the coating in the early stage of corrosion protection 2 The rapid reaction of the Mg phase and dissolution of the Al phase and formation of specific corrosion products such as LDH.
The cold spraying zinc alloy coating is of a single-layer structure, corrosion protection performance of the coating and in-situ generated products in the corrosion process are further improved, the preparation process is simple and effective, and a functional layer is not required to be additionally added in the preparation process.
The cold spraying zinc alloy coating can effectively reduce the consumption of zinc element, and is beneficial to improving the economic benefit of the cold spraying zinc coating; the excellent protective performance can be widely applied to coating protection and repair engineering of steel structures, and can effectively and conveniently solve the corrosion protection problems of power transmission and transformation facilities, high-speed rail facilities, highway facilities and the like.
The present application is further illustrated by the following specific examples.
Example 1: zn2Mg5Al (common ternary alloy powder)
In the embodiment, a cold spray Zn2Mg5Al coating is prepared on the surface of a Q235 substrate, and the specific steps are as follows:
(1) After oil and rust removal treatment, adopting 80-mesh white corundum sand to coarsen the surface of the base material, then using alcohol to wash the surface of the base material, and drying with cold air;
(2) Preparing Zn2Mg5Al alloy powder with mass fractions of 93%, 2% and 5% of Zn, mg and Al by adopting an air atomization method, and selecting spherical alloy powder with D50=20μm as a raw material after multistage screening;
(3) The nitrogen is adopted as carrier gas, the pressure of the carrier gas is regulated to be 0.6MPa, the temperature of the carrier gas is 400 ℃, the spraying distance is 8mm, the moving speed of a spray gun is 240mm/min, the powder feeding speed is 1g/s, the spray gun is perpendicular to the surface of a substrate for spraying, and the thickness of a coating is controlled to be 100 mu m.
Example 2: zn2Mg-5Al
In the embodiment, a cold spray Zn2Mg-5Al coating is prepared on the surface of a Q235 substrate, and the specific steps are as follows:
(1) After oil and rust removal treatment, adopting 80-mesh white corundum sand to coarsen the surface of the base material, then using alcohol to wash the surface of the base material, and drying with cold air;
(2) Preparing Zn2Mg alloy powder with the mass fractions of 98% and 2% of Mg respectively by adopting an air atomization method, preparing Al powder by adopting an air atomization method, screening the Zn2Mg spherical alloy powder with the mass fraction of D50=20μm and D50=5μm pure Al powder as raw materials, taking 95% of Zn2Mg alloy powder and 5% Al powder according to the mass fraction, and uniformly mixing in a mechanical mixer to obtain cold spraying zinc alloy powder Zn2Mg-5Al;
(3) The nitrogen is adopted as carrier gas, the pressure of the carrier gas is regulated to be 0.6MPa, the temperature of the carrier gas is 400 ℃, the powder feeding rate is 1g/s, the distance between a spray gun and a base material is 8mm, the moving rate of the spray gun is 240mm/min, the spray gun is perpendicular to the surface of the base material for spraying, and the thickness of a coating is controlled to be 100 mu m.
Example 3: zn4Mg-5Al
In the embodiment, a cold spray Zn4Mg-5Al coating is prepared on the surface of a Q235 substrate, and the specific steps are as follows:
(1) After oil and rust removal treatment, adopting 80-mesh white corundum sand to coarsen the surface of the base material, then using alcohol to wash the surface of the base material, and drying with cold air;
(2) Preparing Zn4Mg alloy powder with mass fractions of 96% and 4% of Zn and Mg respectively by adopting an air atomization method, preparing Al powder by adopting an air atomization method, screening the Zn4Mg spherical alloy powder with d50=20 mu m and D50=5 mu m pure Al powder as raw materials by adopting a multistage screening method, taking 95% of Zn4Mg alloy powder and 5% Al powder by mass fractions, and uniformly mixing in a mechanical mixer to obtain Zn4Mg-5Al cold-sprayed zinc alloy powder;
(3) The nitrogen is adopted as carrier gas, the pressure of the carrier gas is regulated to be 0.6MPa, the temperature of the carrier gas is 400 ℃, the powder feeding rate is 1g/s, the distance between a spray gun and a base material is 8mm, the moving rate of the spray gun is 240mm/min, the spray gun is perpendicular to the surface of the base material for spraying, and the thickness of a coating is controlled to be 100 mu m.
Comparative example: zn (zinc)
In this example, a cold spray pure Zn coating was prepared on the surface of Q235 substrate, specifically as follows:
(1) After oil and rust removal treatment, adopting 80-mesh white corundum sand to coarsen the surface of the base material, then using alcohol to wash the surface of the base material, and drying with cold air;
(2) Pulverizing by adopting an air atomization method, and selecting pure Zn spherical powder with D50=20μm as a cold spraying raw material after multi-stage screening;
(3) The nitrogen is adopted as carrier gas, the pressure of the carrier gas is regulated to be 0.6MPa, the temperature of the carrier gas is 400 ℃, the spraying distance is 8mm, the moving speed of a spray gun is 240mm/min, the powder feeding speed is 1g/s, the spray gun is perpendicular to the surface of a substrate for spraying, and the thickness of a coating is controlled to be 100 mu m.
The substrates with cold spray zinc coatings prepared in examples 1-3 and comparative examples were cut off, and the cross-sectional morphology was observed, as shown in fig. 1, with a uniform and dense coating, with good bonding to the substrate interface, and without defects of cracks.
The cold spray zinc coatings prepared in examples 1-3 and comparative example were subjected to performance testing, and EIS impedance spectrum measurement was performed on the coating in the soaking process by using a prinston P4000A electrochemical workstation, and the corrosion protection effect of the coating was judged by the impedance spectrum and polarization curve results:
EIS impedance spectroscopy: the corrosion medium adopts 3.5wt% NaCl solution, the scanning frequency range is 10mHz-100kHz, the electrolytic cell adopts a three-electrode system, wherein a platinum electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and a substrate sample with a cold spray zinc coating is used as a working electrode;
polarization curve: the three-electrode system is adopted to measure the polarization curve, wherein the scanning range is-0.5V/OCP to-0.8V/SCE, and the scanning speed is 2mV/s.
The test results of the substrate samples with cold spray zinc coating after 0.5h immersion in 3.5wt% NaCl solution are shown in Table 1 and FIG. 2, and it can be seen from the polarization curve test results of examples 1-3 and comparative example that the self-corrosion potential of examples 1-3 is significantly reduced compared to comparative example and the self-corrosion potential of examples 2-3 is significantly reduced compared to example 1 for an alloyed coating after addition of an appropriate amount of Mg/Al element. From the thermodynamic point of view, the self-corrosion potential is reduced, which indicates that the coating loses electrons and the capability of providing cathodic protection to the substrate is enhanced; the corrosion current density of the alloyed coating is also dynamically reduced compared with that of the pure Zn coating, which means that the consumption rate of the alloyed coating is lower than that of the pure Zn coating in the whole corrosion protection process, and the alloyed coating has longer service life.
TABLE 1 polarization Curve test results
| Comparative example | Example 1 | Example 2 | Example 3 | |
| Corrosion current Density (A/cm) 2 ） | 1.04×10 -4 | 8.21×10 -5 | 4.76×10 -5 | 3.89×10 -5 |
| Corrosion potential (V/SCE) | -1.08 | -1.34 | -1.37 | -1.41 |
When a substrate sample with a cold spray zinc coating after soaking in 3.5wt% NaCl solution for 24 hours is tested, it is obvious from FIG. 3 that the substrate sample of example 2 after soaking for 24 hours has a higher resistance value, which indicates that the cold spray zinc coating prepared by mixing Zn2Mg alloy powder with Al powder has better corrosion resistance; while the resistance value of the coating prepared from Zn2Mg5Al alloy powder in example 1 at the same composition was relatively low, probably due to the Zn/Al/Zn formed in the pure alloy powder 2 Reactivity of Mg ternary eutectic structure compared to Zn/Zn in example 2 2 The binary eutectic structure of Mg is lower, reaction products are formed less, and thus the impedance is relatively lower; further, the resistance value of example 3 is smaller than that of example 2, and the possible reason is that the product is mostly a water-soluble corrosion product of magnesium at a higher Mg content, and the corrosion product of zinc attached to the surface of the coating is smaller, and thus the coating resistance is lower. In addition, all three coatings have higher impedance than the pure zinc coating, which indicates that corrosion products of the three coatings have better protection effect. As can be seen from fig. 4, the phase angle shows that the pure Zn coating has only one time constant, while the alloy coating has two time constants, which indicates that the corrosion product of the pure Zn coating cannot form an effective shielding layer during the 24h soaking process, whereas the corrosion product of the coating surface rapidly forms a shielding layer in the examples, which has an improvement effect on the protection effect of the coating.
After 24 hours of immersion in 3.5wt% NaCl solution, a tightly packed lamellar corrosion product was observed on the coated surface of the substrate sample of example 2, which has a good physical barrier effect, as shown in FIG. 5.
It will be understood that the application of the present application is not limited to the examples described above, but that modifications and variations can be made by those skilled in the art in light of the above description, all of which are intended to be within the scope of the present application.
Claims (10)
1. The cold spraying zinc alloy powder is characterized by being mechanically mixed powder of ZnMg alloy powder and aluminum powder;
the ZnMg alloy powder is prepared by adopting an air atomization powder preparation method, wherein Mg accounts for 0-4% of the mass fraction of the ZnMg alloy powder, and the mass fraction of Mg is not 0%;
the aluminum powder is prepared by adopting an air atomization powder preparation method;
the aluminum powder accounts for 0-30% of the mass fraction of the cold spray zinc alloy powder, and the mass fraction of the aluminum powder is not 0%.
2. The cold sprayed zinc alloy powder according to claim 1, wherein Mg accounts for 2-4% of the ZnMg alloy powder by mass fraction.
3. The cold spray zinc alloy powder according to claim 1, wherein the aluminum powder accounts for 5% -15% of the mass of the cold spray zinc alloy powder.
4. The cold sprayed zinc alloy powder according to claim 1, wherein the ZnMg alloy powder has an average particle diameter of 20 to 50 μm; the average particle diameter of the aluminum powder is 5-15 mu m.
5. A method for preparing the cold spray zinc alloy powder according to any one of claims 1 to 4, comprising the steps of:
preparing ZnMg alloy powder and aluminum powder respectively by an aerosolization powder preparation method;
and mixing the ZnMg alloy powder and the aluminum powder in a mechanical stirring mode to obtain the cold spraying zinc alloy powder.
6. A method for preparing a cold spray zinc alloy coating, which is characterized in that the cold spray zinc alloy powder according to any one of claims 1-4 is adopted to prepare the cold spray zinc alloy coating on the surface of a substrate in a cold spray mode.
7. The method of preparing a cold sprayed zinc alloy coating according to claim 6, wherein the cold spraying mode is a low pressure cold spraying mode.
8. The method of producing a cold sprayed zinc alloy coating according to claim 7, wherein in the cold spraying process, the carrier gas is one of compressed air, nitrogen or helium, the gas pressure is 0.5 to 0.8MPa, the carrier gas temperature is 200 to 600 ℃, the powder feeding rate is 0.5 to 2g/s, the distance between the spray gun and the substrate is 6 to 20mm, and the spray gun moving rate is 200 to 600mm/min.
9. The method of preparing a cold sprayed zinc alloy coating according to claim 6, further comprising the steps of, prior to said cold spraying:
oil and rust removal is carried out on the surface of the base material;
and (3) carrying out sand blasting coarsening pretreatment on the surface of the base material, cleaning by using acetone or alcohol, and drying by cold air.
10. A cold spray zinc alloy coating, characterized in that it is prepared by the method for preparing a cold spray zinc alloy coating according to any one of claims 6 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211572121.4A CN115747573B (en) | 2022-12-08 | 2022-12-08 | Cold spraying zinc alloy powder, coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211572121.4A CN115747573B (en) | 2022-12-08 | 2022-12-08 | Cold spraying zinc alloy powder, coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115747573A CN115747573A (en) | 2023-03-07 |
| CN115747573B true CN115747573B (en) | 2024-02-13 |
Family
ID=85344519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211572121.4A Active CN115747573B (en) | 2022-12-08 | 2022-12-08 | Cold spraying zinc alloy powder, coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115747573B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001164194A (en) * | 1999-12-13 | 2001-06-19 | Nippon Steel Corp | Zinc-rich coating excellent in corrosion-resistant property and coated metal plate |
| CN1651605A (en) * | 2005-03-09 | 2005-08-10 | 沈阳工业大学 | Spray coating technology of magnesium alloy surface protective layer |
| JP2016166395A (en) * | 2015-03-10 | 2016-09-15 | 新日鐵住金株式会社 | Formation method of zinc-containing coating |
| CN107675163A (en) * | 2017-11-14 | 2018-02-09 | 北京科技大学 | The method that the pure zinc of Mg alloy surface/Zinc alloy coated is prepared based on cold spray technique |
| CN111647884A (en) * | 2020-06-09 | 2020-09-11 | 西安建筑科技大学 | Gradient nanocrystalline and ultrafine-grained coating and preparation method thereof |
| CN114181609A (en) * | 2021-12-15 | 2022-03-15 | 江苏科技大学 | Zinc-aluminum-magnesium alloy modified water-based cold-spraying zinc coating and preparation method thereof |
| CN114182249A (en) * | 2021-12-01 | 2022-03-15 | 常州大学 | Method for increasing corrosion resistance of cold spraying double-layer coating |
| CN114574801A (en) * | 2022-03-10 | 2022-06-03 | 福建宏贯路桥防腐科技股份有限公司 | Novel multi-element alloy co-permeation agent and preparation method thereof |
| CN114836713A (en) * | 2020-07-08 | 2022-08-02 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Zn-Al-Cr-Bi multi-element powder co-permeation agent and application thereof |
-
2022
- 2022-12-08 CN CN202211572121.4A patent/CN115747573B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001164194A (en) * | 1999-12-13 | 2001-06-19 | Nippon Steel Corp | Zinc-rich coating excellent in corrosion-resistant property and coated metal plate |
| CN1651605A (en) * | 2005-03-09 | 2005-08-10 | 沈阳工业大学 | Spray coating technology of magnesium alloy surface protective layer |
| JP2016166395A (en) * | 2015-03-10 | 2016-09-15 | 新日鐵住金株式会社 | Formation method of zinc-containing coating |
| CN107675163A (en) * | 2017-11-14 | 2018-02-09 | 北京科技大学 | The method that the pure zinc of Mg alloy surface/Zinc alloy coated is prepared based on cold spray technique |
| CN111647884A (en) * | 2020-06-09 | 2020-09-11 | 西安建筑科技大学 | Gradient nanocrystalline and ultrafine-grained coating and preparation method thereof |
| CN114836713A (en) * | 2020-07-08 | 2022-08-02 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Zn-Al-Cr-Bi multi-element powder co-permeation agent and application thereof |
| CN114182249A (en) * | 2021-12-01 | 2022-03-15 | 常州大学 | Method for increasing corrosion resistance of cold spraying double-layer coating |
| CN114181609A (en) * | 2021-12-15 | 2022-03-15 | 江苏科技大学 | Zinc-aluminum-magnesium alloy modified water-based cold-spraying zinc coating and preparation method thereof |
| CN114574801A (en) * | 2022-03-10 | 2022-06-03 | 福建宏贯路桥防腐科技股份有限公司 | Novel multi-element alloy co-permeation agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 铝和镁对锌铝镁合金凝固组织与力学性能的影响;杨巧燕;汤茂友;刘亚;涂浩;苏旭平;王建华;;稀有金属;40(05);422 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115747573A (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109136828B (en) | Preparation method of Zn-Al-Ni anticorrosive function permeable layer | |
| CN101629287B (en) | Magnesium alloy surface treatment process | |
| CN110144579B (en) | Zinc-based composite coating with rapid repair capability and preparation method and application thereof | |
| CN105039964A (en) | Surface corrosion-resistant and abrasion-resistant composite coating for magnesium alloy and preparation method of surface corrosion-resistant and abrasion-resistant composite coating | |
| CN114182249B (en) | Method for improving corrosion resistance of cold-sprayed double-layer coating | |
| CN101045980A (en) | High aluminium zinc alloy hot dip coating process for iron steel product | |
| CN113088956B (en) | Cold spraying-based corrosion-resistant composite coating and preparation method and application thereof | |
| CN103668043A (en) | Diffusion zincizing coating method | |
| CN102284405B (en) | Production method for zinc-magnesium or zinc-aluminum-magnesium clad steel sheet and zinc-aluminum-magnesium clad steel sheet thereof | |
| CN105463443B (en) | A kind of marine drilling platform corrosion resistant coating production | |
| CN112940554A (en) | Zn-Al coating with sintered neodymium-iron-boron as base body and preparation method thereof | |
| CN100532476C (en) | Surface antiseptic treating agent for cable bridge frame | |
| CN105568208A (en) | Surface treatment method for weathering resistant steel | |
| CN1207438C (en) | Suface-treating agent of steel material and surface-treated steel material | |
| CN114318215B (en) | Manufacturing method of stay cable threaded anchorage powder zinc-aluminum multi-element alloy anti-corrosion coating | |
| CN101186998B (en) | Transmission line pole tower long-lasting anticorrosion coating and its preparation process | |
| CN115747573B (en) | Cold spraying zinc alloy powder, coating and preparation method thereof | |
| Liu et al. | Enhanced corrosion and wear resistance of Zn–Ni/Cu–Al2O3 composite coating prepared by cold spray | |
| CN114481012B (en) | Multielement alloy co-permeation agent for steel member and corrosion prevention process thereof | |
| CN114632949A (en) | Additive manufacturing metal part surface anticorrosion and antifouling composite treatment method | |
| CN109207987B (en) | Mechanical galvanized carbon steel clamping and pressing type pipe fitting and preparation process thereof | |
| CN1114665C (en) | Zinc base water soluble anti-corrosion paint for metal surface and its prepn. method | |
| KR20210077952A (en) | Hot dip alloy coated steel material having excellent anti-corrosion properties and method of manufacturing the same | |
| CN112962089B (en) | Environment-friendly and efficient nickel-free manganese phosphating agent and preparation method and application thereof | |
| CN110004388A (en) | Carbon nano-tube modification rare earth modifies hot-dip galvanized alloy coating for protection against corrosion and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |